Process and composition for the froth flotation beneficiation of iron minerals from iron ores

ABSTRACT

A process and composition are provided for the froth flotation beneficiation of iron minerals from iron ores containing silicate and phosphate minerals, comprising as collectors a combination of a primary amine and a nitrogen compound containing an anionic group selected from methylene carboxylic acid, ethylene phosphoric acid and methylene phosphonic acid.

This application is a division of Ser. No. 888,186, filed July 22, 1986, now abandoned, which in turn is a division of Ser. No. 703,241, filed Feb. 20, 1985, now U.S. pat No. 4,732,667, patented Mar. 22, 1988.

Iron ores are commonly subjected to froth flotation to separate the iron minerals, such as hematite, using fatty acids as a collector. However, the selectivity of fatty acids for the iron minerals is accepted as inadequate.

Nowadays an aliphatic amine is used as a selective collector in froth flotation for many gangue minerals such as silicates. In an initial desliming stage and/or in the main froth flotation stage, starch or a starch derivative is added, as a depressant for the iron minerals.

Japanese patent applications Nos. 58-159,856 and 58-156358 suggest use in froth flotation of an aliphatic diamine in combination with a dimer acid or a beta-amino acid. The advantage is claimed to be an unusual high content of iron in the iron concentrate.

While these methods give adequate beneficiation of the iron minerals, small amounts of phosphate minerals are enriched at the same time in the iron mineral concentrates. These small amounts of phosphate minerals (from about 0.05% by weight of phosphor) turn up as unacceptably high contents of phosphorus in the iron product.

Hellsten and Klingberg, U.S. Pat. No. 4,358,368, patented Nov. 9, 1982, provides a process for the froth flotation of calcium phosphate-containing minerals which comprises carrying out the flotation in the presence of an amphoteric flotation agent having the general formula: ##STR1## wherein: R is a hydrocarbon group having from about seven to about twenty-four carbon atoms;

A is an oxyalkylene group having from two to about four carbon atoms;

R₁ is selected from the group consisting of hydrogen and hydrocarbon groups having from one to about four carbon atoms;

Y is selected from the group consisting of COO⁻ and SO₃ ⁻ ;

n is a number from 0 to 1;

p is a number from 0 to 5;

q is a number from 1 to 2;

and salts thereof.

This collector reagent is disclosed in Examples 4 and 5 to be selective for calcium phosphate present with iron minerals and silicates in waste material from magnetically enriched iron ore.

The process and composition of the present invention provide without a concentrate having a lower content of phosphate minerals without a lowered content of iron mineral. Indeed, the iron content in the concentrate may even be increased.

The invention accomplishes this by utilizing as collectors for the gangue minerals a combination of a primary amine and a nitrogen compound having an anionic group selected from the group consisting of methylene carboxylic acid groups, methylene phosphonic acid groups, and ethylene phosphoric acid groups, including, optionally, as a third ingredient, a depressant for the iron minerals.

FIG. 1 is a flow sheet showing the froth flotation process in accordance with the invention.

The primary amine has the general Formula I:

    R.sub.1 --[OC.sub.n.sbsb.1 H.sub.2n.sbsb.1 ].sub.m.sbsb.1 --[NHC.sub.n.sbsb.2 H.sub.2n.sbsb.2 ].sub.m.sbsb.2 --NH.sub.2 I

in which:

R₁ is a hydrocarbon group having from about six to about eighteen carbon atoms;

n₁ and n₂ are 2 or 3; and

m₁ is from 0 to 4, preferably 0 or 1 and m₂ is from 0 to 2, preferably 0 or 1.

The nitrogen compounds containing an anionic group have the general Formula II: ##STR2## in which: R₂ is a hydrocarbon group having from about one to about twenty-four carbon atoms;

X is a group ##STR3## n₃ is a number from 2 to 4; m₃ is a number from 0 to 4, and can be an average number;

m₄ is 0 or 1;

m₅ is 0 or 1;

m₆ is 0 or 1;

R₃ is selected from the group consisting of hydrogen; hydrocarbon groups having from one to about eighteen carbon atoms; and ##STR4## R₄ is selected from the group consisting of methylene carboxylic acid--CH₂ COOH; methylene phosphonic acid ##STR5## and ethylene phosphoric acid ##STR6## and salts thereof with an inorganic or organic cation.

The anionic group containing compound preferably has a total number of carbon atoms in the hydrocarbon groups of R₂ and R₃ within the range from about twelve to about twenty-five, and m₄ is 1. The number of carbon atoms of each hydrocarbon group in R₂ and R₃ is preferably within the range from about one to about eighteen.

A preferred class of nitrogen compounds containing an antionic group has the general formula III: ##STR7## in which: R₅ is a hydrocarbon group having from about five to about twentyfour carbon atoms;

X is a group ##STR8## n₃ is a number from 2 to 4; m₃ is a number from 0 to 5, and can be an average number;

m₄ is 0 or 1;

m₅ is 0 or 1;

when m₃ and m₄ are 0, m₆ is 0;

p and q are numbers from 1 to 3; preferably, p is 2 or 3;

R₆ and R₇ are selected from the group consisting of hydrogen; hydrocarbon groups having from one to about twelve carbon atoms; and ##STR9## can be taken together as ##STR10## and M is a monovalent inorganic or organic cation or hydrogen.

One such class of compounds encompassed by Formula III which is easy to produce has the general formula: ##STR11## in which R₅, R₆, R₇ and M have the same meaning as in Formula III, p is 2 or 3, and q is 1 to 3.

Another subclass of Formula III compounds having good flotation properties can easily be produced from α-olefins as starting reactants. These compounds have the formula: ##STR12## in which R₅, R₆, R₇ and M have the same meaning as in Formula III, p is 2 or 3 and q is 1 to 3.

Another preferred subclass is obtained from a hydroxyl compound and epichlorohydrin. These compounds have the formula: ##STR13## in which R₅, R₆, R₇, m₃, n₃ and M have the same meaning as in Formula III, p is 2 or 3 and q is 1 to 3.

Another subclass of compounds within Formula III has the formula: ##STR14## in which R₅, R₆, R₇ and M have the same meaning as in Formula III, p is 2 or 3, and q is 1 to 3.

Still another such class of compounds having good flotation properties and easy to produce has the general formula: ##STR15## in which R₅, X, m₃, m₄, m₅, n₃ and M have the same meaning as in Formula III.

Exemplary R₁, R₂, R₃, R₅, R₆ and R₇ hydrocarbon groups include aliphatic hydrocarbon groups (which are preferred as R₁) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, tert-amyl, sec-amyl (R₃ only), hexyl, isohexyl, tert-hexyl, sec-hexyl, heptyl, octyl, isooctyl, 2-ethyl hexyl, nonyl,isononyl, tert-nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, linoleyl, linolenyl, and behenyl; cycloaliphatic hydrocarbon groups, such as cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; and cyclooctyl; and aromatic hydrocarbon groups, such as phenyl, methyl phenyl, dimethyl phenyl, propyl phenyl, butyl phenyl, octyl phenyl, nonyl phenyl, and dodecyl phenyl.

Especially preferred amines of Formula I are those amines in which R₁ is aliphatic and m₂ is 0. These primary amines are known compounds.

Exemplary ##STR16## groups include ethyleneoxy; propyleneoxy-1,2; butyleneoxy-2,3; and butyleneoxy-1,2 (C_(n).sbsb.3 H_(2n).sbsb.3 O only).

Exemplary primary amines include: ##STR17##

Exemplary nitrogen compounds containing an anionic group include: ##STR18##

If mixtures of two or more types of minerals are subjected to froth flotation using two ionic collectors of opposite charge, very often problems occur, since the collectors may interfere with each other. The interference may result in larger reagent consumption, frothing problems, and high losses of the valuable mineral, in this case, the iron mineral. However, in the process of the present invention, none of these drawbacks occurs.

While in general it is more efficient to utilize the primary amine and the anionic group containing collectors together, in admixture, they can be used separately, in sequential steps.

Each of the collectors is normally added in an amount within the range from about 5 to about 250 g per ton of ore, preferably within the range from about 5 to about 100 g per ton of ore.

The compound containing the anionic group can be produced from commercially available starting compounds using known methods, such as disclosed in U.S. Pat. No. 4,358,368, patented Nov. 9, 1982.

The group R₂ is aliphatic is derived from an alcohol, such as Ziegler, Oxo and fatty alcohols, for example, butanol, iso-butanol, secondary-butanol, hexanol, secondary-hexanol, iso-hexanol, 2-ethyl hexanol, octanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

When R₂ is cycloaliphatic or aromatic, cycloaliphatic alcohols and aromatic phenols can be utilized as the starting material. Suitable cycloaliphatic alcohols are cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, and alkylsubstituted cycloalcohols. Suitable aromatic phenols include synthetically manufactured monoand dialkyl-substituted phenols, such as octyl phenol, nonyl phenol, dodecyl phenol, and dibutyl phenol, and tributyl phenol.

The R₃, R₆ and R₇ hydrocarbon group or hydrogen and/or the R₄ acid group can be introduced using a compound having the Formulae IV, V, VI or VII: ##STR19## in which R₃, R₄, R₆, R₇, m₃, m₄, m₅ and m₆ are as above in Formulae II and III. Tertiary amines in which R₃, R₆ and R₇ is methyl, 2-ethyl hexyl, decyl, or an isomer thereof or phenyl and R₄ is ##STR20## are preferred.

When R₃, R₆ or R₇ is the group having the formula ##STR21## the tertiary amine can be obtained by reacting two moles of the alkylene oxide having the formula ##STR22## with one mole of the amine having the formula H₂ NR₄.

The groups [C_(n).sbsb.3 H_(2n).sbsb.3 O]_(m).sbsb.3 and [CH₂ CHOHCH₂ ]_(m).sbsb.4 can be introduced by conventional methods by reacting a suitable starting compound with alkylene oxide and epichlorohydrin. The group ##STR23## can be introduced by using ethylene diamine, diethylene triamine, triethylene tetramine and the corresponding propylene amines as well as alkylsubstituted derivates thereof as reactants. As an alternative, it is possible to use acrylonitrile as a reactant and then hydrogenate.

The flotating properties of the amphoteric compound can be further improved by the presence of a hydrophobic secondary collector, preferably in the form of a polar, water insoluble, hydrophobic substance with affinity to the mineral particles coated with the amphoteric compound. The amphoteric compound is usually added in an amount of from 10 to 1000, preferably from 50 to 500 grams per metric ton of ore and the polar, water insoluble, hydrophobic substance in an amount from 0 to 1000, preferably from 5 to 750 grams per metric ton of ore. In the case where the amphoteric compound is used in combination with the hydrophobic substance the ratio between them may be varied within wide limits but normally it is within the interval from 1:20 to 20:1, preferably from 1:5 to 5:1. The water insoluble hydrophobic substance, which according to the invention may be characterized as a secondary collector, consists preferably of a polar substance. If desired, a conventional emulsifier dissolved in a hydrocarbon can also be added in order to obtain a stable emulsion in water and a good distribution. The emulsifier may be a nonionic surface active compound, which in the case it is water insoluble is to be included in the polar substance. Suitable polar components are water insoluble soaps such as calcium soaps; water insoluble surface active alkylene oxide adducts; organic phosphate compounds, such as tributyl phosphate, tri-(2-ethylhexyl) phosphate; and esters of carboxylic acids, such as tributyl ester and tri(2-ethyl hexyl) ester of NTA as well as dioctylphthalate.

In the froth flotation process of the invention the amphoteric collector can also be and preferably is utilized in combination with a depressant.

The depressant can be any conventional mineral depressant, such as a hydrophilic polysaccharide. Suitable hydrophilic polysaccharides include cellulose esters, such as carboxymethyl cellulose and sulphomethyl cellulose; cellulose ethers, such as methyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, and ethyl hydroxyethyl cellulose; the hydrophylic natural gums, such as gum arabic, gum karaya, gum tragacanth; and gum ghatti; the alginates; and starch, such as corn starch, and starch derivatives, such as carboxymethyl starch and starch phosphate. Polysaccharides having anionic groups are preferred.

The depressant should be present in the mineral pulp before each flotation process in a sufficient amount to prevent the iron mineral from floating. Normally, the amount of depressant is within the range from about 10 to about 1000 grams per ton ore, but this amount is not critical.

In flotation pH regulators can also be added, as well as activators. In most flotations, the pH is of importance in obtaining a good separation, and process to optimize the separation of different minerals by the selection of a suitable pH. The character of the amphoteric compound varies considerably with pH. At a pH below 6, it is mainly cationic, while it is chiefly anionic at pHs above 10, and zwitterionic at pH's between 6 and 10. In the separation of ore containing apatite and silicate or apatite and calcite, an excellent, selective enrichment is obtained, if the flotation process is carried out at a pH from about 8 to about 11. Conventional frothers and activators can also be added. Each ore has to be treated in accordance with its own chemical and physical composition.

The primary amine and the anionic group containing compound can be combined and marketed as a collector composition, ready for addition to the ore at the froth flotation step, in the desired proportion to each other. The amines can be in liquid form, in solution in water or a water-miscible inert solvent. The amines can be solubilized as the acid salt with an inorganic acid, such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid or formic acid, or the secondary or tertiary amine as the salt of the carboxylic acid or phosphoric acid group with an alkali metal hydroxide such as sodium hydroxide or ammonia. Solid amines can be marketed in solid form.

The relative proportions of the primary amine and secondary or tertiary amine are not critical, and can normally be within the range from 4:1 to 1:4, preferably from 2:1 to 1:2.

In the process shown in the flow sheet of FIG. 1, the primary amine and tertiary amine collector are present together in the rougher flotation step, which is a preferred process due to the simplicity of the equipment.

Compounds according to the invention generally show good properties in flotation of oxide or salt type minerals, such as apatite may well be used when enriching iron minerals from phosphor containing ores in combination with a primary amine as a silicate collector.

FIG. 1 shows a flow sheet of such a froth flotation process.

As see in FIG. 1, in Stage I the iron ore, together with water, sodium hydroxide and sodium silicate, are ground to a particle size suitable for froth flotation. The ground ore slurry then passes to Stage II, where the ore is pretreated with starch and sodium hydroxide to adjust pH, resulting in slime formation. The slime rises to the surface of the slurry, and is removed. The ore is then conditioned for several minutes in Stage III, with addition of more sodium hydroxide to adjust pH, and starch, and then in Stage IV the primary amine and secondary and/or tertiary amine collectors are added with more sodium hydroxide to adjust pH, and conditioned for several more minutes. The slurry is subjected to a rougher flotation in Stage V. The gangue at the surface is removed as Froth Product I, and the bottom iron mineral concentrate passed to the Stage VI conditioning, after addition of more primary amine, and sodium hydroxide to adjust pH. After conditioning for several minutes, there follows a second froth flotation, separating a Froth Product 2, and recovering the iron mineral concentrate product.

If desired, the primary amine and secondary or tertiary amine can be used in separate steps, shown in dashed lines in FIG. 1. In this case, primary amine only is added with sodium hydroxide in Stage IVa, followed by a rougher flotation Stage Va, and then secondary or tertiary amine is added with sodium hydroxide in Stage IVb, followed by a rougher flotation in Stage Vb. The other stages are as in solid lines in FIG. 1.

The froth flotation processing conditions form no part of the invention and are entirely conventional. The conditioning and flotation steps can be carried out at room or ambient temperature, but elevated temperatures can be used, up to about 100° C., or the volatilization temperature of the amine, if lower. The pH is usually on the alkaline side, and preferably between pH 8 and pH 12.

The following Examples represent preferred embodiments of the process of the invention.

EXAMPLES 1 to 13

Froth flotations were carried out in accordance with the flow sheet shown in FIG. 1.

An iron ore containing Fe 34%, Si 23.9% and P 0.044%, mainly present as hematite 49%, silicate (quartz) 51%, and apatite 0.24%, was crushed to particles less than 1.7 mm in diameter and homogenized. From the homogenized material portions of 600 grams each were taken out. The portions were further ground in a laboratory rod mill for 30 minutes together with 400 ml of water, 0.40 g sodium hydroxide and 0.27 g water glass (38% sodium silicate by weight, weight ratio SiO₂ /NaO₂ =3.22, 41.0° Be).

The particle distribution was such that 97% by weight passed through a 32 μm mesh sieve.

An aqueous mineral pulp 8 liters in volume was prepared from each portion of the ground material. Temperature and pH were adjusted to about 20° C. and 10.5, respectively. 0.0675 g of prehydrolyzed corn starch was added, and the whole was conditioned in a paddle mixer for 2 minutes.

The conditioned pulp was allowed to settle for 3 minutes, and then the slime was siphoned off. The deslimed pulp was divided into four fractions, and each fraction transferred to a flotation cell and diluted with water to a volume of 0.5 liter. The pH was adjusted to 10.5 with sodium hydroxide, followed by the addition of 0.0675 g of the prehydrolyzed corn starch. After conditioning for 2 minutes, and a final pH adjustment of 11.0, the secondary or tertiary amine and primary amine collectors were added. The amount of the primary amine was 0.0067 g, and the amount of the secondary or tertiary amine is given in Table I. After an additional conditioning for 2 minutes, a rougher flotation was carried out, giving a Froth Product 1 and a bottom iron mineral concentrate. The pH was again adjusted to 11 with sodium hydroxide, 0.0067 g of primary amine was added to the bottom concentrate, and the whole conditioned for 2 minutes, followed by another froth flotation, giving a Froth Product 2, and iron mineral concentrate. The primary and secondary or tertiary amines used and the results obtained are shown in Table I.

                                      TABLE I                                      __________________________________________________________________________     Example                                                                        No.  Anionic Collector               g/ton                                                                              Primary Amine Collector               __________________________________________________________________________     Control                                                                             None                            --  (C.sub.8-10 H.sub.17-21)O(CH.sub.                                              2).sub.3NH.sub.2                            ##STR24##                      54  C.sub.10 H.sub.21NH.sub.2             2                                                                                    ##STR25##                      54  C.sub.10 H.sub.21 O(CH.sub.2).sub                                              .3 NH(CH.sub.2).sub.3 NH.sub.2        3                                                                                    ##STR26##                      54  (C.sub.8-10 H.sub.17-21)O(CH.sub.                                              2).sub.3NH.sub.2                      4                                                                                    ##STR27##                      54  (C.sub.8-10 H.sub.17-21)O(CH.sub.                                              2).sub.3NH.sub.2                      5                                                                                    ##STR28##                      54  (C.sub.8-10 H.sub.17-21)O(CH.sub.                                              2 ).sub.3NH.sub.2                     6                                                                                    ##STR29##                      54  (C.sub.8-10 H.sub.17-21)O(CH.sub.                                              2).sub.3NH.sub.2                      7    (C.sub.8 H.sub.17).sub.2NCH.sub.2 PO.sub.3 H.sub.2                                                             10  (C.sub.8-10 H.sub.17-21)O(CH.sub.                                              2).sub.3NH.sub.2                      8                                                                                    ##STR30##                      20  (C.sub.8-10 H.sub.17-21)O(CH.sub.                                              2).sub.3NH.sub.2                      9                                                                                    ##STR31##                      54  (C.sub.8-10 H.sub.17-21)O(CH.sub.                                              2).sub.3NH.sub.2                      10   (C.sub.8 H.sub.17).sub.2NCH.sub.2 CH.sub.2 OPO.sub.3 H.sub.2                                                   54  (C.sub.8-10 H.sub.17-21)O(CH.sub.                                              2).sub.3NH.sub.2                      11                                                                                   ##STR32##                      54  (C.sub.8-10 H.sub.17-21)O(CH.sub.                                              2).sub.3NH.sub.2                      12                                                                                   ##STR33##                          (C.sub.8-10 H.sub.17-21)O(CH.sub.                                              2).sub.3NH.sub.2                      13                                                                                   ##STR34##                      54  (C.sub.8-10 H.sub.17-21)O(CH.sub.                                              2).sub.3NH.sub.2                      __________________________________________________________________________                     Deslimed                                                                             Iron mineral concentrate                                 Example                                                                             Feed  Slimes                                                                              Pulp       % Fe      % SiO.sub.2                                                                         % P P distribution in                No.  % P Assay                                                                            % Wt.                                                                               % P Assay                                                                            % Wt.                                                                               Grade                                                                              Recovery                                                                             Assay                                                                               Assay                                                                              % of flotation                   __________________________________________________________________________                                                   feed                             Control                                                                             0.043 32.2 0.033 37.9 66.0                                                                               74.7  5.8  0.048                                                                              81.6                             1    0.045 32.4 0.037 38.8 67.0                                                                               77.7  4.3  0.034                                                                              52.0                             2    0.044 32.4 0.035 41.1 65.2                                                                               80.0  6.7  0.034                                                                              58.6                             3    0.045 32.4 0.037 38.7 67.4                                                                               77.8  3.8  0.029                                                                              44.9                             4    0.043 32.4 0.034 40.7 66.0                                                                               80.2  5.7  0.024                                                                              42.3                             5    0.043 31.9 0.035 38.2 67.8                                                                               77.6  3.3  0.029                                                                              46.3                             6    0.045 29.7 0.039 39.6 67.2                                                                               79.3  4.2  0.033                                                                              47.8                             7    0.044 29.9 0.034 37.6 67.4                                                                               75.6  3.6  0.034                                                                              52.9                             8    0.045 29.7 0.038 40.9 66.3                                                                               80.8  5.4  0.032                                                                              48.4                             9    0.045 29.7 0.038 39.4 66.8                                                                               78.5  4.8  0.025                                                                              36.6                             10   0.046 28.4 0.042 39.2 66.5                                                                               77.8  5.4  0.034                                                                              44.9                             11   0.044 28.3 0.038 38.9 66.3                                                                               76.8  5.0  0.028                                                                              39.7                             12   0.044 30.8 0.036 38.9 66.7                                                                               77.3  5.1  0.030                                                                              48.2                             13   0.045 31.4 0.035 40.3 65.4                                                                               78.5  4.2  0.030                                                                              52.1                             __________________________________________________________________________

By comparison with the Control, it is evident that Examples 1 to 11 carried out in accordance with the invention yield iron mineral concentrates with a low % P assay and a P distribution considerably lower than in the Control. This is achieved without undue losses of iron (see % Fe grade and recovery), and also with some improvement in the silicate flotation. Some of the tests show an iron recovery that is essentially superior to the results reported in Japanese patent applications Nos. 58-159,856 and 58-156,358.

The compound and the process of the invention is further illustrated by the following Example.

EXAMPLE 14

A.

The amide ##STR35## was prepared by reacting 272 grams (1 mole) of ##STR36## with 104 grams (1 mole) of aminoethyl ethanolamine H₂ NCH₂ CH₂ --NHCH₂ CH₂ OH. The released methanol was distilled off at the end of reaction. After the reaction the reaction mixture was titrated and the amount of basic nitrogen was determined. The yield of the amide was about 93%.

The amide in an amount of 72 grams (0.2 mole) was then reacted with 35 grams of polyphosphoric acid at 85° C. for two hours.

Titration of the anionic group containing surface active compound confirmed the formation of ##STR37## The total yield was about 69%, and the reaction product obtained was a highly viscous mass, which was soluble in water after neturalization.

B.

The epoxide ##STR38## in an amount of 104 grams (0.48 moles) was reacted with aminoethyl ethanolamine in an amount of 25 grams (0.24 moles) for two hours at 70° C. with formation of the tertiary amine: ##STR39## The amination degree was determined by titration of tertiary nitrogen and was found to be about 91%.

50 grams (0.093 moles) of the tertiary amine was then reacted with 26 grams of polyphosphoric acid at 70° C. for two hours.

Titrimetric determination of the anionic group containing surface active compound confirmed the formation of the compound: ##STR40## The product obtained was a highly viscous mass, soluble in water after neutralization.

C.

Froth flotations were carried out in accordance with the flow sheet shown in FIG. 1, using the compounds of A and B.

An iron ore containing Fe 34%, Si 23.9% and P O.044%, mainly present as hematite 49%, silicate (quartz) 51%, and apatite 0.24%, was crushed to particles less than 1.7 mm in diameter and homogenized. From the homogenized material portions of 600 grams each were taken out. The portions were further ground in a laboratory rod mill for 30 minutes together with 400 ml of water, 0.40 g sodium hydroxide and 0.27 g water glass (38% sodium silicate by weight, weight ratio SiO₂ NaO₂ =3.22, 41.0° Be).

The particle distribution was such that 97% by weight passed through a 32μ mesh sieve.

An aqueous mineral pulp 8 liters in volume was prepared from each portion of the ground material. Temperature and pH were adjusted to about 20° C. and 10.5, respectively. 0.0675 g of prehydrolyzed corn starch was added, and the whole was conditioned in a paddle mixer for 2 minutes.

The conditioned pulp was allowed to settle for 3 minutes, and then the slime was siphoned off. The deslimed pulp was divided into four fractions and each fraction transferred to a flotation cell and diluted with water to a volume of 0.5 liter. The pH was adjusted to 10.5 with sodium hydroxide, followed by the addition of 0.0675 g of the prehydrolyzed corn starch. After conditioning for 2 minutes, and a final pH adjustment to 11.0, the anionic collector and primary amine collectors were added. The amount of the primary amine was 0.0067 g, and the amount of the anionic collector is given in Table I. After an additional conditioning for 2 minutes, a rougher flotation was carried out, giving a Froth Product 1 and a bottom iron mineral concentrate. The pH was again adjusted to 11 with sodium hydroxide 0.0067 g of primary amine was added to the bottom concentrate, and the whole conditioned for 2 minutes, followed by another froth flotation, giving a Froth Product 2, and iron mineral concentrate. The primary amines and anionic group-containing compounds used and the results obtained are shown in Table I.

D. Pure minerals composed of fluorapatite, calcite, scheelite, magnesite, quartz, olivine, and fluorite, respectively, were subjected to froth flotation. Firstly, the minerals were ground and wet-screened, and the fractions +250-400 μm were selected, to be used in the froth flotation trials. These fractions were added in an amount of 0.2 ml to test tubes having a diameter of 15 mm and a length of 120 mm. 10 ml of an aqueous fluid containing 0.01 g/1 of a collector according to Table II, and having a pH of 8 or 11 were added, whereafter the minerals were conditioned for 5 minutes during stirring.

After the conditioning the water phase was sucked off and water under a pressure of 7 atm and saturated with air was injected via a lance. When the pressure of the water was reduced, the air was liberated and a froth flotation process took place. The amount of floated material was determined visually. The results are shown in Tables III and IV below.

                                      TABLE I                                      __________________________________________________________________________     Example                                                                        No.  Anionic Collector        g/ton                                                                               Primary Amine Collector                     __________________________________________________________________________     Control                                                                             None                     --   (C.sub.8-10 H.sub.17-21)O(CH.sub.2).sub                                        .3NH.sub.2                                  14A                                                                                  ##STR41##               40   (C.sub.8-10 H.sub.17-21)O(CH.sub.2).sub                                        .3NH.sub.2                                  14B                                                                                  ##STR42##               42   (C.sub.8-10 H.sub.17-21)O(CH.sub.2).sub                                        .3NH.sub.2                                  __________________________________________________________________________     Feed         Deslimed                                                                             Iron mineral concentrate                                    Example                                                                             % P Slimes                                                                             Pulp      % Fe      % SiO.sub.2                                                                         % P P distribution in                    No.  Assay                                                                              % Wt.                                                                              % P Assay                                                                            % Wt.                                                                              Grade                                                                              Recovery                                                                             Assay                                                                               Assay                                                                              % of flotation                       __________________________________________________________________________                                               feed                                 Control                                                                             0.043                                                                              32.2                                                                               0.033 37.9                                                                               66.0                                                                               74.7  5.8  0.048                                                                              81.6                                 14A  0.049                                                                              32.0                                                                               0.037 44.4                                                                               62.7                                                                               81.1  9.4  0.031                                                                              58.7                                 14B  0.046                                                                              32.0                                                                               0.031 37.4                                                                               65.7                                                                               71.5  5.2  0.024                                                                              40.9                                 __________________________________________________________________________

                  TABLE II                                                         ______________________________________                                         Example                                                                        No.    Collector                                                               ______________________________________                                         14C                                                                                    ##STR43##                                                              14D                                                                                    ##STR44##                                                              14E                                                                                    ##STR45##                                                              14F                                                                                    ##STR46##                                                              14G                                                                                    ##STR47##                                                              Control                                                                                ##STR48##                                                              B                                                                                      ##STR49##                                                              ______________________________________                                    

                  TABLE III                                                        ______________________________________                                         % Floated mineral, pH 8                                                               Example No.       Con-    Con-                                                 14C  14D    14E     14F  14G  trol A                                                                               trol B                              ______________________________________                                         Fluorapatite                                                                            85     100    100   50   100  15    35                                Calcite  85     50     25    50   50   25     0                                Dolomite 15     65     25    --   --    0     0                                Fluorite 100    100    100   --   --   100   100                               Scheelite                                                                               15     65     15    --   --    0    15                                Baryte   25     75     75    --   --   25    15                                Quartz   25     15     100   100  15    0    15                                Magnesite                                                                               15      0      0    --   --    0     0                                Olivine  25     85     100   --   --   15     0                                ______________________________________                                    

                  TABLE IV                                                         ______________________________________                                         % Floated mineral, pH 11                                                              Example No.       Con-    Con-                                                 14C  14D    14E     14F  14G  trol A                                                                               trol B                              ______________________________________                                         Fluorapatite                                                                            25     100    85    100  100  15    25                                Calcite   0     25     85    25   25   0     0                                 Dolomite 25     25     85    --   --   15    0                                 Fluorite 65     85     100   --   --   85    100                               Scheelite                                                                               25     65     75    --   --   25    15                                Baryte   15     25     65    --   --   0     15                                Quartz    0      0     15    25   10   0     0                                 Magnesite                                                                                0      0      0    --   --   0     0                                 Olivine   0     15      0    --   --   0     0                                 ______________________________________                                     

Having regard to the foregoing disclosure, the following is claimed as the patentable and inventive embodiments thereof:
 1. A flotation agent composition comprising a primary amine having the formula:

    R.sub.1 --[OC.sub.n.sbsb.1 H.sub.2n.sbsb.1 ]m.sub.1 --[NHC.sub.n.sbsb.2 H.sub.2n.sbsb.2 ]m.sub.2 --NH.sub.2                       I

in which: R₁ is a hydrocarbon group having from about six to about eighteen carbon atoms; n₁ and n₂ are 2 or 3; and m₁ is from 0 to 4, and m₂ is from 0 to 2,;and a nitrogen compound containing an anionic group having the formula: ##STR50## in which: R₂ is a hydrocarbon group having from about one to about twentyfour carbon atoms; X is a group ##STR51## n₃ is a number from 2 to 4; m₃ is a number from 0 to 4, and can be an average number; m₄ is 0 or 1; m₅ is 0 or 1; m₆ is 0 or 1; R₃ is selected from the group consisting of hydrogen; hydrocarbon groups having from one to about eighteen carbon atoms; and ##STR52## R₄ is selected from the group consisting of methylene carboxylic acid--CH₂ COOH; methylene phosphonic acid ##STR53## and ethylene phosphoric acid ##STR54## and salts thereof with an inorganic or organic cation.
 2. A composition according to claim 1 in which R₁ is aliphatic hydrocarbon and m₂ is
 0. 3. A composition according to claim 1 in which the total number of carbon atoms in the R₂ and R₃ hydrocarbon groups are within the range from about twelve to about twenty-five, and m₄ is
 1. 4. A composition according to claim 1 in which the number of carbon atoms in the R₂ and R₃ hydrocarbon groups are within the range from about one to about eighteen.
 5. A flotation agent composition comprising a primary amine having the formula:

    R.sub.1 --[OC.sub.n.sbsb.1 H.sub.2n.sbsb.1 ]m.sub.1 --[NHC.sub.n.sbsb.2 H.sub.2n.sbsb.2 ]m.sub.2 --NH.sub.2                       I

in which: R₁ is a hydrocarbon group having from about six to about eighteen carbon atoms; n₁ and n₂ are 2 or 3; and m₁ is from 0 to 4, and m₂ is from 0 to 2,;and a nitrogen compound containing an anionic group having the formula: ##STR55## in which: R₅ is a hydrocarbon group having from about five to about twenty-four carbon atoms; X is a group ##STR56## n₃ is a number from 2 to 4; m₃ is a number from 0 to 5, and can be an average number; m₄ is 0 or 1; m₅ is 0 or 1; m₆ is 0 or 1; when m₃ and m₄ are 0, m₆ is 0; p and q are numbers from 1 to 3; R₆ and R₇ are selected from the group consisting of hydrogen; hydrocarbon groups having from one to about twelve carbon atoms; and ##STR57## can be taken together as ##STR58## and M is a monovalent inorganic or organic cation or hydrogen.
 6. A flotation agent composition according to claim 5, in which the nitrogen compound has the formula: ##STR59## in which R₅, R₆, R₇ and M have the same meaning as in Formula III, claim 5, p is 2 or 3, and q is 1 to
 3. 7. A flotation agent composition according to claim 5, in which the nitrogen compound has the formula: ##STR60## in which R₅, R₆, R₇ and M have the same meaning as in Formula III, p is 2 or 3 and q is 1 to
 3. 8. A flotation agent composition according to claim 5, in which the nitrogen compound has the formula: ##STR61## in which R₅, R₆, R₇, m₃, n₃ and M have the same meaning as in Formula III, p is 2 or 3 and q is 1 to
 3. 9. A flotation agent composition according to claim 5, in which the nitrogen compound has the formula: ##STR62## in which R₅, R₆, R₇ and M have the same meaning as in Formula III, p is 2 or 3, and q is 1 to
 3. 10. A flotation agent composition according to claim 5, in which the nitrogen compound has the formula: ##STR63## in which R₅, X, m₃, m₄, m₅, n₃ and M have the same meaning as in claim
 5. 11. An anionic group containing nitrogen compound having the Formula III: ##STR64## in which: R₅ is a hydrocarbon group having from about five to about twenty-four carbon atoms;X is a group ##STR65## n₃ is a number from 2 to 4; m₃ is a number from 0 to 5, and can be an average number; m₄ is 0 or 1; m₅ is 0 or 1; m₆ is 0 or 1; when m₃ and m₄ are 0, m₆ is 0; p and q are numbers from 1 to 3; R₆ and R₇ are selected from the group consisting of hydrogen; hydrocarbon groups having from one to about twelve carbon atoms; and ##STR66## can be taken together as ##STR67## and M is a monovalent inorganic or organic cation or hydrogen.
 12. A compound according to claim 11 having the formula: ##STR68## in which R₅, R₆, R₇ and M have the same meaning as in Formula III, claim 11, p is 2 or 3, and q is 1 to
 3. 13. A compound according to claim 11 having the formula: ##STR69## in which R₅, R₆, R₇ and M have the same meaning as in Formula III, p is 2 or 3 and q is 1 to
 3. 14. A compound according to claim 11 having the formula: ##STR70## in which R₅, R₆, R₇, m₃, n₃ and M have the same meaning as in Formula III, p is 2 or 3 and q is 1 to
 3. 15. A compound according to claim 11 having the formula: ##STR71## in which R₅, R₆, R₇ and M have the same meaning as in Formula III, p is 2 or 3, and q is 1 to
 3. 16. A compound according to claim 11 having the formula: ##STR72## in which R₅, X, m₃, m₄, m₅, n₃ and M have the same meaning as in claim
 11. 17. An anionic group containing nitrogen compound having the formula II ##STR73## in which: R₂ is a hydrocarbon group having from about one to about twentyfour carbon atoms;X is a group ##STR74## n₃ is a number from 2 to 4; m₃ is a number from 0 to 4, and can be an average number; m₄ is 0 or 1; m₅ is 0 or 1; m₆ is 0 or 1; R₃ is selected from the group consisting of hydrogen; hydrocarbon groups having from one to about eighteen carbon atoms; and ##STR75## R₄ is ethylene phosphoric acid ##STR76## and a salt thereof with an inorganic or organic cation. 